Thiazoles and thiazolines



Patented July 11, 1944 UNITED STATES 'rnmzomzs AND 'rnmzomms Winfield Scott, Akron, om, assignor a Windoot Corporation, Wilmington, DeL, a corporation of Delaware No Drawing. Application March 6, 1942, Serial No. 433,632

Claims. (in. 260-302) This invention relates to new chemical compounds having the general formula where R. is a thiazyl or thiazolyl radical derived respectively from a thiazole or a thiazoline and R1 is an aryl group. The thiazole group of the above formula may be that of an arylene thlazyl such as only one of the following: Z-benzothiazyl, 6-ch1or-2-benzothiazyl, 4-phenyl-2-benzothiazyl, 4-methyl-2-benzothiazyl, 6-ethoxy-2-benzothiazyl, 6-methoxy-2-benzothiazyl, 6-chlor-5-nitro-2- benzothiazyl, 6-hydroxy-2-benzothiazyl, fi-nitroz-benzothiazyl, 5-chlor-2-benzothiazyl, tetrahydro-2-benzothiazyl, the alpha and beta naphthothiazyls, both substituted and unsubstituted, and other alkyl, aryl, nitro, amino, hydroxy, halo, alkoxy, etc. derivatives of the arylene thiazyl group. The thiazyl group may also be Z-thiazyl or a substituted thlazyl group, such as 4-methyl-2-thiazyl, 4-,5-dimethyl-2-thiazyl, 5-methyl-2-thlazyl, 5-phenyl-2-thiazyl, 5-benzyl-2-thiazyl, 4- methoxy-S-methyl thiazyl, 5(4-chlorphenyl) -2- thiazyl or 4-chlor-2-thiazyl and other thiazyls substituted in the 4-, or 5-, or 4- and 5-positions with an allql, alkoxy, thialkyl, aryl, aralkyl, chloro or nitro, etc. group. The mercaptothiazolyl may be 2-thiazolyl, 4-methy1-2-thiazolyl, bethyl-Z-thiazolyl, 4-benzyl-2-thiazoyl and 5- chloro-2-thiazolyl, or other groups in which the 4- or 5-position or both may be substituted with a usual substituent.

The R1 of the formula is a part of the sulfonamide group. In spite of the fact that it is usual to refer to such compounds as benzene sulfonamide, toluene sulfonamide, etc. R1 is referred to herein as a radical. It may be phenyl,

tolyl, alpha naphthyl, beta naphthyl, xenyl, etc. and may form groups such as benzene-i-chlorosulfonylamido, toluene-Z-hydroxy 4 sulfonylamido, naphthalene disulfonylamido, xylene sulfonylamldo mixture or a mixture of any one or more of the sulfonylamido compounds.

The compounds of this invention accelerate USES.

The compounds of this invention may be pre- :forming! them coniprises reacting the sulfon- 65 amide with a z-methylolmercaptothiaaole or mercaptothiazoline.

Examples of preparing the compound follow:

Example 1 The new compound may be prepared in a solvent such as alcohol, as follows: Sixteen and seven-tenths grams (0.1 mol) of 2-mercaptobenzothiazole, 17.1 grams (0.1 mol) of p-toluene 1o sulfonamide and 8.5 grams (slightly in excess of (0.1 mol) of 37% formaldehyde were added to 300 cc. of alcohol and warmed for a few minutes. To the solution was then added 25 ml. of concentrated hydrochloric acid. The mixture was then 15 refluxed for two hours, then allowed to stand at room temperature. Soon yellow leaflets began to separate. After filtering, washing and drying these crystals they were found to melt at 161 162 C.

2o Emmlple 2 The material of Example 1 can also be made without the use of an acid catalyst. Thirty three and four-tenths grams of 2-mercaptobenzothiazole, 34.2 grams of p-toluene sulfonamide and 6.0 grams of paraformaldehydewere added to 300 cc. of benzene in a flask equipped with a stirrer, thermometer and reflux containing a water trap in the condensate return. when no more water was formed, the refluxing was stopped, and flask and contents allowed to cool. Yellow leaflets melting at 161-162 C. separated out in a yield of 86%. The analysis for nitrogen, calculated at 8.00%; found, 7.67%. This indicates the reaction of equal mols of the three reactants and the formula is presumed to be that given above.

40 azole for 2-mercaptobenzothiazole in the procedure of Example 2, the reaction proceeds smoothly to give the corresponding derivative. In this experiment, one-tenth molar quantities were used in a solution of 100 cc. of toluene. The

the vulcanization of rubber and may have other theoretical amount of water of condensation was obtained and the crystalline reaction product after recrystallizing from toluene, melted at 157 C.

Erwmple 4 Allwl or unsubstituted mercaptothiazoles undergo the reaction with formaldehyde and a sulfonamide as readily as arylene mercaptothiazoles. Thirteen-and one-tenth grams of 4-methyl-2- mercaptothiazole, 17.1 grams of p-toluene sulfonamide and 3.0 grams of paraformaldehyde 2 e mscamoa were heoted to the refluxing temperatureot toluene in 100 cc. of this solvent. The reaction proceeds smoothly and the crystalline reaction product melted at 184' C. after recrystallization tron: toluene at 185' C.

Eraniple 5 Twenb three and eight-tenths grams (0.2 mol) of 2-mercupthisaoline and 34.2 grams.(0.3 mol) of p-toluene sulfonylamide are added to 250 cc.

'. of benzene in r. suitable reaction vessel eqmpped withustirrerandarefluxivlthawatertrapin thereturn. 'lhesuspenisonisheatedtoreiluxing of the solvent when five drops ofconcentrated .hydrochloricncidisadded. Sixmmsoiparaon cooling and is obtained as white crystals. After crystallization from benzene, the product was iound to melt at 126-128 C.

I claim:

1. As a. new composition 01 matter, a. compound selected from the group consisting of the 2 (arylsulionylamide methylene thio) thiazoles and the 2-(a .ry1sultony1amide-methylenethio)-thlazolines.

1o 2.1m new compounds, the z-(arylsuliouylamido-methylene-thio) -thia.zoles.

3. As new compounds, the 2-'(ary1sulionylamido-methylene-thio) -thiazolines.

4. As new compounds, the 2-(arylsulfony1- l6 amido-me'thylene-thio) -arylenethiazoles.

5. As new compounds, the z-(arylsulfonylamido-methylene-thio) -benzothiazoles.

WINFELD SCO'I'I'.

CERTIFICATE OF CORRECTION. Patent No. 2,355,595. July 11, 191 1;.

' wnwnzm SCOTT.

It is hereby certified thet error appears in the printed specification of the above numbered potent requiring correction as follows: Page 1, first column, line 5, for flfiazolyl" read. --dihyd.rothiazy1- line 7 for "thia-' zoie" reed --'thia'zy l--; line 8 Strikeout "that of an lines 27 to 30 inelusive, strike out nle mercaptothiazoly i may be 2-thiazo1e, lp-me thyl-Z- thia'zolyl, L-ethyl-Z- thiazoIyI h-benzyl-Z-thiazoyl and 5 1 r -2- thiazo1y1" endinsert instead -:The dihydr'othiazyl group inthe formula may be Z-dihydrothizwl, hw fi r y h-ethyL-Z-dihydrothiazyl, h-benz'yl- 2 dihydrothiaz yl, and 5-ohloro-2dihydr'othiazyl-; pageEQfirst column,1ine

1 before atter" insert --and-.-'; and that the said Letters Patent shouldbe read with this correctiontherein that the some may conform to the record of the ease in the Patent Ofiioe.

Signed and sealed this 5rd day of October, A.-p. 191m.

A ,Leslie Frazer (Seal) I Acting Commissioner of Patents. 

